US20060067029A1 - Multilayered structure, multilayered structure array and method of manufacturing the same - Google Patents
Multilayered structure, multilayered structure array and method of manufacturing the same Download PDFInfo
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- US20060067029A1 US20060067029A1 US11/220,693 US22069305A US2006067029A1 US 20060067029 A1 US20060067029 A1 US 20060067029A1 US 22069305 A US22069305 A US 22069305A US 2006067029 A1 US2006067029 A1 US 2006067029A1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/228—Terminals
- H01G4/232—Terminals electrically connecting two or more layers of a stacked or rolled capacitor
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/01—Manufacture or treatment
- H10N30/08—Shaping or machining of piezoelectric or electrostrictive bodies
- H10N30/085—Shaping or machining of piezoelectric or electrostrictive bodies by machining
- H10N30/088—Shaping or machining of piezoelectric or electrostrictive bodies by machining by cutting or dicing
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/50—Piezoelectric or electrostrictive devices having a stacked or multilayer structure
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/80—Constructional details
- H10N30/87—Electrodes or interconnections, e.g. leads or terminals
- H10N30/875—Further connection or lead arrangements, e.g. flexible wiring boards, terminal pins
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N39/00—Integrated devices, or assemblies of multiple devices, comprising at least one piezoelectric, electrostrictive or magnetostrictive element covered by groups H10N30/00 – H10N35/00
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/01—Manufacture or treatment
- H10N30/06—Forming electrodes or interconnections, e.g. leads or terminals
- H10N30/063—Forming interconnections, e.g. connection electrodes of multilayered piezoelectric or electrostrictive parts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/43—Electric condenser making
- Y10T29/435—Solid dielectric type
Definitions
- Multilayered structures in each of which insulating (dielectric) layers and electrode layers are alternately formed, are utilized not only for multilayered capacitors but also for various uses such as piezoelectric pumps, piezoelectric actuators, and ultrasonic transducers.
- MEMS micro electro mechanical systems
- insulating regions 106 in which no electrode is formed are provided for insulating the electrode layers from either of the side electrodes.
- the insulating regions 106 do not expand or contract even when a voltage is applied to the multilayered structure 100 . On this account, there is a problem that stress is concentrated on the part and the part becomes easy to break.
- a multilayered structure shown in FIG. 16 is known as one using another interconnection method in the multilayered structure.
- the multilayered structure 200 shown in FIG. 16 has plural piezoelectric material layers 201 , plural internal electrode layers 202 , insulating films 203 formed on one end surfaces of the respective internal electrode layers 202 , and two side electrodes 204 and 205 .
- the end surfaces on the opposite sides are covered by the insulating films 203 and the layers are insulated from either one of the side electrodes 204 and 205 , and thereby, a circuit equivalent to the multilayered structure 100 shown in FIG. 15 can be realized.
- the multilayered structure 200 since the internal electrode layers 202 are formed over the entire surfaces of the piezoelectric material layers 201 , the multilayered structure 200 is more advantageous than the multilayered structure 100 shown in FIG. 15 in expression of piezoelectric performance. Further, as described above, since the stress concentration as in the insulating regions 106 ( FIG. 15 ) is not generated in the multilayered structure 200 , the life of multilayered structure hardly becomes shorter.
- the insulating layers are formed by electrophoresis only on the exposed parts of the internal electrode layer plates and the electrostriction materials nearby.
- glass is used as a material of the insulting layers.
- glass films formed by electrophoresis are aggregates of cluster particles, and they are sparse films. Accordingly, in order to obtain a sufficient withstand voltage, the thickness of the insulating layer is required to be several tens of microns.
- a first object of the present invention is to narrow pitches of a multilayered structure array by reducing thickness of coatings for insulating internal electrode layers from side electrodes. Further, a second object of the present invention is to improve the productivity of multilayered structures and multilayered structure arrays by easily forming such coatings.
- a method of manufacturing a multilayered structure includes the steps of: (a) forming a first dielectric layer; (b) disposing a conducting material on the first dielectric layer to form a first internal electrode layer; (c) forming a second dielectric layer on the first internal electrode layer; (d) disposing a conducting material on the second dielectric layer to form a second internal electrode layer; (e) forming at least one groove in a workpiece including the first dielectric layer, the first internal electrode layer, the second dielectric layer and the second internal electrode layer formed at steps (a) to (d) to produce plural structures partially connected to one another and expose the end surfaces of the first and second internal electrode layers on a first side surface region and a second side surface region different from the first side surface region of each structure respectively, and selectively forming conducting material films on end surfaces of the first and second internal electrode layers; and (f) causing at least one part of each of the first and second conducting material films formed at step (e) to have insulation to form a first coating and a second
- FIG. 1 is a sectional view showing a multilayered structure according to a first embodiment of the present invention
- FIGS. 2A to 2 C are perspective views for explanation of a method of manufacturing a multilayered structure and a multilayered structure array according to the first embodiment of the present invention
- FIGS. 3A to 3 C are perspective views for explanation of the method of manufacturing the multilayered structure and the multilayered structure array according to the first embodiment of the present invention
- FIGS. 4A to 4 C are perspective views for explanation of the method of manufacturing the multilayered structure and the multilayered structure array according to the first embodiment of the present invention
- FIGS. 5A to 5 C are perspective views for explanation of the method of manufacturing the multilayered structure and the multilayered structure array according to the first embodiment of the present invention
- FIGS. 6A to 6 C are partially sectional perspective views for explanation of the method of manufacturing the multilayered structure and the multilayered structure array according to the first embodiment of the present invention
- FIG. 7 is a schematic diagram showing a configuration of a film forming device using an aerosol deposition method
- FIG. 8 is a sectional view showing a structure of an ultrasonic probe using the multilayered structure array shown in FIG. 6C ;
- FIG. 9 is a sectional view showing a structure of a multilayered structure according to a second embodiment of the present invention.
- FIGS. 10A and 10B are diagrams for explanation of a principle of a method of forming a magnetic film
- FIGS. 11A to 11 D are perspective views for explanation of a method of manufacturing the multilayered structure and a multilayered structure array according to the second embodiment of the present invention.
- FIGS. 12A to 12 C are perspective views for explanation of the method of manufacturing the multilayered structure and the multilayered structure array according to the second embodiment of the present invention.
- FIG. 13 is a perspective view for explanation of the method of manufacturing the multilayered structure and the multilayered structure array according to the second embodiment of the present invention.
- FIGS. 14A and 14B are perspective views for explanation of a modified example of the method of manufacturing the multilayered structure and the multilayered structure array according to the second embodiment of the present invention.
- FIG. 15 is a sectional view for explanation of an interconnection method in a conventional multilayered structure.
- FIG. 16 is a sectional view for explanation of another interconnection method in the conventional multilayered structure.
- FIG. 1 is a sectional view showing a multilayered structure according to one embodiment of the present invention.
- the multilayered structure 1 is a columnar structure having a bottom surface with sides on the order of 0.2 mm to 1.0 mm, for example.
- a piezoelectric material as a ferroelectric material is used as a dielectric material.
- the multilayered structure 1 includes plural piezoelectric material layers 10 , plural internal electrode layers 11 a and 11 b , and coatings 12 formed on one ends of the respective internal electrode layers 11 a and 11 b .
- the multilayered structure 1 may include two side electrodes 13 a and 13 b formed on the side surfaces of the stacked plural piezoelectric material layers 10 .
- the multilayered structure 1 may include an upper electrode 14 and a lower electrode 15 formed as external electrodes on upper and lower bottom surfaces of the stacked plural piezoelectric material layers 10 , respectively. As shown in FIG. 1 , the upper electrode 14 is connected to one side electrode 13 b and the lower electrode 15 is connected to the other side electrode 13 a .
- the shape of the bottom of the multilayered structure 1 is not limited to a square, but rectangular or other shapes may be adopted. Further, in the embodiment, although the side electrodes are disposed on opposed two side surfaces 1 a and 1 b , the regions in which the side electrodes are disposed are not limited to two opposed side surfaces as long as they are electrically insulated from each other.
- Each piezoelectric material layer 10 is a piezoelectric material film having a thickness on the order of 100 ⁇ m.
- PZT Pb(lead) zirconate titanate
- PbTiO 3 as principal chemical compositions is used as the piezoelectric material.
- a ternary or above solid solution formed by adding at least one of Pb (Mg 1/3 Nb 2/3 )O 3 , Pb (Ni 1/3 Nb 2/3 )O 3 , Pb (Zn 1/3 Nb 2/3 )O 3 as a third component to such a binary solid solution may be used.
- the piezoelectric material PLZT (lanthanum-doped lead zirconate titanate) formed by adding lanthanum oxide to PZT, or a non-lead piezoelectric material such as KNbO 3 or bismuth series material may be used.
- the piezoelectric material layer 10 may contain not only those principal components but also elements such as germanium (Ge), silicon (Si), lithium (Li), bismuth (Bi), boron (B), and lead (Pb), which are contained in auxiliaries to be used for growing crystals by heat treatment.
- Each of the internal electrode layers 11 a and 11 b has a thickness of about 2 ⁇ m.
- hardly-oxidizable conducting materials may be desirably used, and platinum (Pt) is used in the embodiment.
- each of the coatings 12 is a film having a thickness of about 10 ⁇ m, and provided for insulating the internal electrode layers 11 a and 11 b from the side electrodes 13 a and 13 b , respectively.
- the coatings 12 are formed by forming films of a conducting material by using an electrodeposition method on predetermined end surfaces of the internal electrode layers 11 a and 11 b , and then, causing the films to have insulation by oxidizing them. Accordingly, at least the surfaces of the coatings 12 (surfaces in contact with the side electrodes 13 a or 13 b ) are covered by metal oxide as an insulating material.
- nickel (Ni) is used as the conducting material as a raw material of the coatings 12 , and at least the surfaces of the coatings 12 are nickel oxide. Although the entire regions of the coatings 12 have been made to have insulation in FIG. 1 , the conducting material may be left inside of the coatings 12 .
- the electrodeposition method includes an electroplating, or a deposition method utilizing electrophoresis power.
- the end surfaces of the internal electrode layers 11 a are covered by the coatings 12
- the end surfaces of the internal electrode layers 11 b are covered by the coatings 12 .
- the internal electrode layers 11 a are insulated from the side electrode 13 a located on the side surface 1 a
- the internal electrode layers 11 b are insulated from the side electrode 13 b located on the side surface 1 b . Since the electrodes of the multilayered structure are thus formed, the stacked plural layers are electrically connected in parallel.
- the respective piezoelectric material layers 10 expand and contract by the piezoelectric effect.
- the multilayered structures employing such piezoelectric material layers as dielectric layers can be used for piezoelectric pumps, piezoelectric actuators, ultrasonic transducers for transmitting and receiving ultrasonic waves in an ultrasonic probe, and so on. Further, in the structure having the multilayered structure as described above, since areas of the opposed electrodes can be made larger than that in a single layer structure, electrical impedance can be made lower. Therefore, compared to the single layer structure, the multilayered structure operates more efficiently for the applied voltage.
- FIGS. 2A to 6 C are diagrams for explanation of the method of manufacturing a multilayered structure and a multilayered structure array according to the embodiment.
- an exhaust pipe 47 In the film forming chamber 46 , an exhaust pipe 47 , a nozzle 48 , and a movable stage 49 are provided.
- the exhaust pipe 47 is connected to a vacuum pump and exhausts air from the film forming chamber 46 .
- the nozzle 48 sprays the aerosol generated in the aerosol generating container 42 and introduced through the aerosol lead-in part 44 into the film forming chamber 46 toward the substrate 20 .
- the substrate 20 is mounted on the movable stage 49 that is movable in a three-dimensional manner, and the relative position between the substrate 20 and the nozzle 48 is adjusted by controlling the movable stage 49 .
- the particles (raw material powder) injected from the nozzle 48 and accelerated to a high speed with high kinetic energy collide against the substrate 20 are deposited thereon.
- a PZT monocrystal powder having an average particle diameter of 0.3 ⁇ is mixed in auxiliaries such as germanium, silicon, lithium, bismuth, boron, and lead used for growing crystals by heat treatment according to need and placed within the aerosol generating container 42 shown in FIG. 7 , and the film forming device is driven. Thereby, the piezoelectric material layer 21 as shown in FIG. 2A is formed on the substrate 20 .
- metal coatings are selectively formed on predetermined end surfaces of the plural electrode layers 22 .
- a material of coatings a relatively easily-oxidizable metal is used, and nickel (Ni) is used in the embodiment.
- interconnections 26 are formed on the end surfaces of the electrode layers 22 by using a method such as wire bonding or solder joint from every other layer in each structure 25 as shown in FIG. 3A .
- the surface on which the interconnections are formed is desirably a surface other than the surface on which the coatings 12 are to be formed, and they are formed on the front side surface in the drawing in the embodiment.
- nickel coatings are selectively formed on predetermined end surfaces of the plural electrode layers 22 .
- interconnections 31 are formed on the end surfaces of the electrode layers 22 , on which the nickel coating 27 is not formed, by using a method such as wire bonding or solder joint.
- electroplating is performed by using a plating solution containing nickel ions to attach nickel to the end surfaces of the electrode layers 22 on which the interconnections have been formed.
- the surfaces on which the nickel coatings 27 have been previously formed are covered by the epoxy resin 28 , no film is formed on the end surfaces of the electrode layers 22 even if the interconnections 31 are formed.
- nickel coatings 32 of about 10 ⁇ m are formed on each structure 30 . Then, the interconnections 31 are removed.
- the plural structures 30 are immersed in an organic solvent such as acetone to dissolve the epoxy resin 28 . Thereby, plural structures 30 in which nickel coatings 27 and 32 have been formed in a staggered manner on the plural electrode layers 22 are obtained. Further, the nickel coatings 27 and 30 are oxidized by heat treating the plural structures 30 for 30 minutes in air in an atmosphere at 800° C. Thereby, the plural structures 30 on which insulating films 33 have been formed are obtained as shown in FIG. 4C .
- the heat treatment on the piezoelectric material layers may be simultaneously performed by controlling the temperature and time of that heat treatment.
- each multilayered structure 36 can be made to have a square form by setting the pitch and width of dicing nearly equal to those formed between the plural structures 30 .
- a multilayered structure array ( 1 - 3 composite) 2 including plural multilayered structures 1 ( FIG. 1 ) arranged in a two-dimensional manner can be manufactured.
- the lower part of the plural multilayered structures 36 fixed by the epoxy resin 37 are ground as shown in FIG. 6A , and then, the plural multilayered structures 36 are separated from one another by dissolving the epoxy resin using an organic solvent. According to need, lower electrodes or insulating films 38 shown in FIG. 6B may be formed before dissolving the epoxy resin.
- a multilayered structure array including plural multilayered structures 1 arranged in a one-dimensional manner can be also manufactured.
- dicing has been performed in the direction perpendicular to the longitudinal sides of the rectangular shapes as shown in FIG. 5C .
- the direction may not be the perpendicular direction as long as each multilayered structure after separation includes two side electrodes.
- the piezoelectric material layers in the workpiece 23 have been formed by using the AD method.
- the same work piece can be fabricated by stacking PZT plate materials on which the metal thin films as electrode layers have been formed or stacking the PZT thick films and electrode layers using other methods than the AD method (e.g., green sheet method).
- the surrounding parts of the plural structures 30 and the grooves between the structures are filled with an epoxy resin and the resin is cured.
- the plural structures 30 are separated from one another by grinding the lower part of the plural structures 30 .
- insulating films are formed on the end surfaces of one side electrodes exposed on the lower bottom surface of the epoxy resin, and further, a common electrode is formed.
- the surrounding parts of the plural structures 30 and the grooves between the structures are filled with an epoxy resin and the resin is cured.
- the filling material urethane resin, silicone rubber, or the like may be used other than that.
- the lower part of the plural structures are ground 30 and the plural structures 30 may be separated from one another, and then, the epoxy resin is dissolved by an organic solvent.
- lower electrodes or insulating films 38 shown in FIG. 6B may be formed before dissolving the epoxy resin.
- the coatings formed on the side regions of the multilayered structure for insulating the side electrodes from the internal electrode layers are formed by forming films of a conducting material using an electrodeposition method and oxidizing the films. That is, since dense metal oxide covers the end surfaces of the internal electrodes, even the insulating films are as thin as about 10 ⁇ m, sufficient insulation performance can be exerted. Further, since the film thickness can be controlled, narrow pitch arrangement in a multilayered structure can be easily accommodated.
- FIG. 8 is a sectional view showing an ultrasonic probe using the multilayered structures according to the embodiment as an ultrasonic transducer array.
- this ultrasonic probe includes a multilayered structure array 2 shown in FIG. 6C , interconnections 51 drawn from the multilayered structure array 2 , an acoustic matching layer 52 of Pyrex glass or the like disposed at one bottom surface side (e.g., the common electrode 39 side) of the multilayered structure array 2 , and a backing material 53 of an epoxy resin containing metal powder or the like disposed at the other bottom surface side.
- a casing for accommodating the ultrasonic probe is omitted.
- the electrical impedance can be lowered and impedance matching with a transmitting and receiving circuit can be improved using the above-mentioned multilayered structures as ultrasonic transducers used for an ultrasonic probe, application efficiency of voltage can be improved and detection sensitivity of ultrasonic waves can be made higher. Further, since the number of ultrasonic transducers to be mounted can be increased by narrowing the pitches of element arrangement in the ultrasonic transducer array, scanning density of ultrasonic waves can be made higher and the transmission and reception directions can be controlled more precisely. Therefore, the image quality of ultrasonic images can be improved by making solving power higher. Alternatively, the entire ultrasonic probe can be downsized while maintaining the conventional ultrasonic transmission and reception performance.
- FIG. 9 is a sectional view showing a structure of the multilayered structure according to the second embodiment.
- This multilayered structure 3 has internal electrodes 11 a and 11 b in the multilayered structure 1 shown in FIG. 1 and, in place of the coatings 12 , internal electrodes 61 a and 61 b and coatings 62 .
- Other constitution is the same as that of the multilayered structure 1 shown in FIG. 1 .
- the coatings 62 are formed by forming films of a conducting material on predetermined end surfaces of the internal electrode layers 61 a and 61 b , and then, making the films to have insulation by oxidizing them.
- the method of forming coatings differs from the method in the first embodiment. That is, in the embodiment, films are formed on the end surfaces of the internal electrode layers using magnetophoresis power in place of electrophoresis power.
- conducting materials of different types are disposed such that a conducting material (first conducting materials 63 ) having magnetism extends to a side surface on which the coatings 62 are to be formed and a conducting material (second conducting materials 64 ) having no magnetism extends to a side surface on which the coatings 62 are not to be formed. Further, as a raw material of the coatings 62 before insulation, a conducting material having magnetism is used.
- FIGS. 10A and 10B are diagrams for explanation of a principle of a method of forming insulating films by magnetophoresis.
- a suspension 6 in which particles of a conducting material having magnetism (hereinafter, referred to as magnetic particles) 4 are dispersed in a liquid 5 is placed.
- a liquid having relatively low viscosity such as water, alcohol, toluene, or xylene is desirably used.
- a laminated structure including plural piezoelectric material layers 10 and internal electrode layers 61 a and 61 b is put into the suspension 6 .
- the magnetic particles 4 are attracted by the first conducting materials 63 having magnetism according to the magnetophoresis power, and adhere to the end surfaces of the first conducting materials 63 .
- the magnetic films 65 can be selectively formed on one end surfaces of the respective internal electrode layers 61 a and 61 b .
- the first conducting material 63 magnetic conducting material
- the magnetic particle 4 magnetic conducting material
- the magnetic particle 4 can be attached to the first conducting material 63 relatively strongly. Further, in the case of using the combination (B), the handling of the magnetic particles 4 when the suspension 6 is prepared is easy, and the power of migration is high and practical. Furthermore, in the case of using the combination (C), the step of placing the first conducting material 63 on the piezoelectric material layer 10 can be simplified. When the materials are determined, an appropriate combination may be selected in consideration of the size and shape of multilayered structure, the compatibility with the raw material of piezoelectric material layer, the manufacturing facility, or the like. Especially, it is necessary to note the relationship between heat treatment temperature for oxidizing the magnetic films 65 later and Curie points of the first conducting material 63 and the magnetic particle 4 .
- the magnetic particle 4 a relatively easily-oxidizable magnetic material such as iron or nickel is used.
- a combination of tungsten steel as the first conducting materials 63 , platinum as the second conducting materials 64 , and iron (Fe) as the magnetic particle 4 is adopted. It is desirable that the particle diameter of the magnetic particle 4 is made as small as possible so as to evenly cover the end surfaces of the internal electrode layers 61 a and 61 b (e.g. about 1 ⁇ m or less).
- FIGS. 11A to 13 a method of manufacturing the multilayered structure and the multilayered structure array according to the second embodiment of the present invention will be described by referring to FIGS. 11A to 13 .
- a workpiece in which plural piezoelectric material layers and internal electrode layers each containing two kinds of conducting materials are stacked, is fabricated.
- a piezoelectric material layer 71 is formed on a substrate 70 using the AD method as shown in FIG. 11A .
- an electrode layer 72 is formed by alternately disposing the first conducting materials 63 and the second conducting materials 64 in band forms on the piezoelectric material layer 71 .
- films of the first conducting materials 63 (tungsten steel) are formed by performing sputtering in the magnetic field using a metal mask in which slit-like openings have been formed at substantially equal widths and intervals to the width of the multilayered structure 3 .
- films of the second conducting materials (platinum) 64 are formed by performing sputtering or vacuum deposition using the metal mask after shifting the substrate 70 by a distance substantially equal to the width of the multilayered structure 3 .
- the widths of the first conducting materials 63 and the second conducting materials 64 may be made narrower than the width of the multilayered structure 3 at both ends of the electrode layer 72 .
- epitaxial growth utilizing crystal magnetic anisotropy and shape magnetic anisotropy may be performed.
- the piezoelectric material layer 71 is formed using AD method on the electrode layer 72 .
- an electrode layer 73 is formed by alternately disposing the first conducting materials 63 and the second conducting materials 64 in band forms on the piezoelectric material layer 71 .
- the locational relationship between the first conducting materials 63 and the second conducting materials 64 is made opposite to the locational relationship between them in the electrode layer 72 .
- the method of forming the first conducting materials 63 and the second conducting materials 64 is the same as that in the electrode layer 72 .
- FIGS. 11A to 11 D are repeated at required times and the piezoelectric material layer 71 is formed on the uppermost position, and thereby, a workpiece 74 shown in FIG. 12A is formed. Subsequently, the substrate 70 is removed by grinding or peeling from the workpiece 74 .
- a heat treatment step of the workpiece 74 at predetermined temperature e.g., 500° C. to 1000° C.
- predetermined temperature e.g., 500° C. to 1000° C.
- the workpiece 74 is separated into plural rectangular structures that are partially connected by dicing the workpiece at the substantially central parts of the first conducting materials 63 and substantially central part of the second conducting materials 64 in the longitudinal direction of the conducting materials.
- FIG. 12B in the respective rectangular structures 75 , the locational relationships between the first conducting materials 63 and the second conducting materials 64 in the internal electrode 61 a and the internal electrode 61 b are opposite to each other.
- the contour of the workpiece 74 may be shaped such that the end surfaces of the first conducting materials 63 and the second conducting materials 64 may be positively exposed on the side surfaces of the workpiece 74 .
- the magnetic films 76 are oxidized by heat treating the plural structures 75 on which the magnetic films 76 have been formed for 30 minutes in air in an atmosphere at 800° C.
- the structures 75 on which insulating films have been formed on the predetermined end surfaces of internal electrodes can be obtained.
- the steps of manufacturing a multilayered structure array or single multilayered structure from those structures 75 are the same as those have been described in the first embodiment by referring FIGS. 4C to 6 C.
- FIG. 14A two kinds of the first and second conducting materials 63 and 64 are arranged in band forms such that the boundary positions between the first conducting materials 63 and the second conducting materials 64 may overlap between electrode layers 81 and electrode layers 82 , which will be formed alternately.
- dicing is performed at those boundaries (broken line positions in FIG. 14A ).
- FIG. 14B since the insulating films are formed in a staggered manner on two side surfaces opposed with grooves in between in the case where the electrode layers are thus disposed, the plural multilayered structures can be arranged with narrower pitches.
- the arrangement of the two kinds of conducting materials that form the internal electrode layers are not necessarily band forms as shown in FIGS. 11B, 11D and 14 A, but an arbitrary arrangement may be adopted in accordance to the shape (e.g., cylindrical shape) or arrangement (e.g., concentric or random arrangement) of multilayered structures to be fabricated. That is, it is essential only that the conducting materials having magnetism be disposed at the side surface side where the insulating films are formed. In this case, two kinds of patterns of conducting materials can be formed using a metal mask. Further, the multilayered structures may be shaped or separated so as to be in arbitrary shapes or arrangement using the sandblasting method.
- the first conducting material 63 and the second conducting material 64 that form the internal electrode layers metals or alloys both having magnetism at normal temperature but having different Curie points are used. That is, multilayered structures 75 shown in FIG. 12B are fabricated by employing a material “A” having Curie point T CA as the first conducting materials 63 on which the coatings 62 are formed, and a material “B” having Curie point T CB (T CB ⁇ T CA ) as the second conducting materials 64 on which no coating 62 is formed.
- T CA Curie point
- T CB ⁇ T CA Curie point T CB
- the range of choice of materials that can be used as conducting materials can be expanded.
- the expression of magnetism may be controlled not only with Curie point, but also with structural phase transition temperature or glass transition point.
- coatings can be easily formed on the end surfaces of internal electrode layers using magnetophoresis. Accordingly, even in the case where opposed electrodes for electrophoresis are difficult to be disposed because of size or arrangement of multilayered structures in the multilayered structure array, coatings can be easily formed on the end surfaces of internal electrode layers of each multilayered structure.
- oxidization treatment has been performed in order to make the coatings of the conducting materials covering the end surfaces of the internal electrode layers to have insulation
- not only the oxidization treatment but also nitriding treatment, fluorination treatment, or sulfuration treatment may be used.
- fluorination treatment nickel films are formed on the end surfaces of the internal electrode layers, the nickel films are chloridized using hydrochloric acid, and then, fluorine is allowed to act thereon in an atmosphere at 150° C. Thereby, nickel fluoride (NiFe 2 ) having insulation can be formed.
- dicing has been performed while not completely separating the workpiece shown in FIGS. 2C and 12A or the like in order to hold the arrangement of the plural multilayered structures in a finished product.
- the manufacturing process may be advanced with the substrate used at the time of workpiece formation mounted.
- the dicing may be performed to the lower bottom surface of the workpiece.
- the plural structures can be completely separated from one another by removing the substrate by peeling or grinding.
Abstract
Description
- 1. Field of the Invention
- The present invention relates to a multilayered structure in which insulating layers and electrode layers are alternately stacked, a multilayered structure array in which plural multilayered structures are arranged, and a method of manufacturing the multilayered structure or the multilayered structure array.
- 2. Description of a Related Art
- Multilayered structures, in each of which insulating (dielectric) layers and electrode layers are alternately formed, are utilized not only for multilayered capacitors but also for various uses such as piezoelectric pumps, piezoelectric actuators, and ultrasonic transducers. In recent years, with the developments of MEMS (micro electro mechanical systems) related devices, elements each having such a multilayered structure have been microfabricated still further and packaged more densely.
- In microfabrication of an element having opposed electrodes, since the smaller the area of the element is made, the smaller the capacity between the electrodes becomes, a problem that the electrical impedance of the element rises occurs. For example, when the electrical impedance rises in a piezoelectric actuator, the impedance matching cannot be taken with a signal circuit for driving the piezoelectric actuator and power becomes difficult to be supplied, and thereby, the performance as the piezoelectric actuator is degraded. Alternatively, in an ultrasonic transducer using a piezoelectric element, oscillation intensity of ultrasonic wave is dropped. Accordingly, in order to enlarge the capacity between electrodes while microfabricating the element, plural piezoelectric material layers and plural electrode layers are alternatively stacked. This is because the capacity between electrodes of the entire element can be made larger by connecting the stacked plural layers in parallel.
- In such a multilayered structure, in order to connect the plural internal electrode layers to one another, interconnection is performed on the side surfaces of the multilayered structure.
FIG. 15 is a sectional view for explanation of a general interconnection method of a multilayered structure. Themultilayered structure 100 includes pluralpiezoelectric material layers 101, pluralinternal electrode layers side electrodes internal electrode layers 102 are formed such that one end thereof may extend to one wall surface of the multilayered structure and connected to theside electrode 104 and insulated from theside electrode 105. Further, theinternal electrode layers 103 are formed such that one end thereof may extend to the other wall surface of the multilayered structure and connected to theside electrode 105 and insulated from theside electrode 104. By applying a potential difference between theside electrode 104 and theside electrode 105, an electric field is applied to thepiezoelectric material layers 101 disposed between theinternal electrode layers 102 and theinternal electrode layers 103, and thepiezoelectric material layers 101 expand and contract by the piezoelectric effect. - By the way, as shown in
FIG. 15 , in the layers in which theinternal electrode layers insulating regions 106 in which no electrode is formed are provided for insulating the electrode layers from either of the side electrodes. Theinsulating regions 106 do not expand or contract even when a voltage is applied to themultilayered structure 100. On this account, there is a problem that stress is concentrated on the part and the part becomes easy to break. - A multilayered structure shown in
FIG. 16 is known as one using another interconnection method in the multilayered structure. Themultilayered structure 200 shown inFIG. 16 has pluralpiezoelectric material layers 201, pluralinternal electrode layers 202,insulating films 203 formed on one end surfaces of the respectiveinternal electrode layers 202, and twoside electrodes internal electrode layers 202, the end surfaces on the opposite sides are covered by theinsulating films 203 and the layers are insulated from either one of theside electrodes multilayered structure 100 shown inFIG. 15 can be realized. - As shown in
FIG. 16 , in themultilayered structure 200, since theinternal electrode layers 202 are formed over the entire surfaces of thepiezoelectric material layers 201, themultilayered structure 200 is more advantageous than themultilayered structure 100 shown inFIG. 15 in expression of piezoelectric performance. Further, as described above, since the stress concentration as in the insulating regions 106 (FIG. 15 ) is not generated in themultilayered structure 200, the life of multilayered structure hardly becomes shorter. - However, in order to fabricate the
multilayered structure 200, theinsulating films 203 should be formed on every other end surface of theinternal electrode layer 202 exposed at each side surface of themultilayered structure 200. Currently, theinsulating films 203 is often formed by using brushing, printing, or photolithography technology, and there is a problem that the productivity is low according to those methods. Further, it is very difficult according to those methods to form insulating films on a two-dimensional array in which plural multilayered structures are arranged with narrow pitches. As another method, as disclosed in Japanese Patent Examined Application Publication JP-B2-61-32835, on exposed side end surfaces of internal electrode layer plates of electrostriction effect elements, the insulating layers are formed by electrophoresis only on the exposed parts of the internal electrode layer plates and the electrostriction materials nearby. In JP-B2-61-32835, glass is used as a material of the insulting layers. However, glass films formed by electrophoresis are aggregates of cluster particles, and they are sparse films. Accordingly, in order to obtain a sufficient withstand voltage, the thickness of the insulating layer is required to be several tens of microns. However, in the case where an ultrasonic transducer array is fabricated, it becomes a problem that ultrasonic transducers cannot be laid out with narrow pitches due to such thickness of the insulating layer. - The present invention is achieved in view of the above-mentioned problems. A first object of the present invention is to narrow pitches of a multilayered structure array by reducing thickness of coatings for insulating internal electrode layers from side electrodes. Further, a second object of the present invention is to improve the productivity of multilayered structures and multilayered structure arrays by easily forming such coatings.
- In order to solve the above-mentioned problems, a multilayered structure according to one aspect of the present invention includes a first internal electrode layer; a dielectric layer formed on the first internal electrode layer; a second internal electrode layer formed on the dielectric layer; a first coating formed on an end surface of the first internal electrode layer in a first side surface region of the multilayered structure and containing one of metal oxide, metal nitride, metal fluoride and metal sulfide in at least one part thereof; and a second coating formed on an end surface of the second internal electrode layer in a second side surface region different from the first side surface region of the multilayered structure and containing one of metal oxide, metal nitride, metal fluoride and metal sulfide in at least one part thereof.
- Further, a multilayered structure array according to one aspect of the present invention includes plural multilayered structures arranged in a one-dimensional manner or a two-dimensional manner, and each of the plural multilayered structures includes: a first internal electrode layer; a dielectric layer formed on the first internal electrode layer; a second internal electrode layer formed on the dielectric layer; a first coating formed on an end surface of the first internal electrode layer in a first side surface region of the multilayered structure and containing one of metal oxide, metal nitride, metal fluoride and metal sulfide in at least one part thereof; and a second coating formed on an end surface of the second internal electrode layer in a second side surface region different from the first side surface region of the multilayered structure and containing one of metal oxide, metal nitride, metal fluoride and metal sulfide in at least one part thereof.
- Furthermore, a method of manufacturing a multilayered structure according to the present invention includes the steps of: (a) forming a first dielectric layer; (b) disposing a conducting material on the first dielectric layer to form a first internal electrode layer; (c) forming a second dielectric layer on the first internal electrode layer; (d) disposing a conducting material on the second dielectric layer to form a second internal electrode layer; (e) forming at least one groove in a workpiece including the first dielectric layer, the first internal electrode layer, the second dielectric layer and the second internal electrode layer formed at steps (a) to (d) to produce plural structures partially connected to one another and expose the end surfaces of the first and second internal electrode layers on a first side surface region and a second side surface region different from the first side surface region of each structure respectively, and selectively forming conducting material films on end surfaces of the first and second internal electrode layers; and (f) causing at least one part of each of the first and second conducting material films formed at step (e) to have insulation to form a first coating and a second coating.
- According to the present invention, coatings containing a metal material are formed on the end surfaces of internal electrodes to be insulated from side electrodes and the coatings are caused to have insulation. Therefore, insulating films can be made further thinner while maintaining the withstand voltage thereof. Further, coatings can be easily formed on the end surfaces of internal electrodes even in a region where the distance between opposed side surfaces is narrow by using electrophoresis or magnetophoresis power. Accordingly, the plural multilayered structures in an multilayered structure array can be easily arranged with narrow pitches, and the productivity can be improved significantly for the multilayered structure, the multilayered structure array, an ultrasonic probe utilizing such a multilayered structure array as ultrasonic transducers, and so on.
-
FIG. 1 is a sectional view showing a multilayered structure according to a first embodiment of the present invention; -
FIGS. 2A to 2C are perspective views for explanation of a method of manufacturing a multilayered structure and a multilayered structure array according to the first embodiment of the present invention; -
FIGS. 3A to 3C are perspective views for explanation of the method of manufacturing the multilayered structure and the multilayered structure array according to the first embodiment of the present invention; -
FIGS. 4A to 4C are perspective views for explanation of the method of manufacturing the multilayered structure and the multilayered structure array according to the first embodiment of the present invention; -
FIGS. 5A to 5C are perspective views for explanation of the method of manufacturing the multilayered structure and the multilayered structure array according to the first embodiment of the present invention; -
FIGS. 6A to 6C are partially sectional perspective views for explanation of the method of manufacturing the multilayered structure and the multilayered structure array according to the first embodiment of the present invention; -
FIG. 7 is a schematic diagram showing a configuration of a film forming device using an aerosol deposition method; -
FIG. 8 is a sectional view showing a structure of an ultrasonic probe using the multilayered structure array shown inFIG. 6C ; -
FIG. 9 is a sectional view showing a structure of a multilayered structure according to a second embodiment of the present invention; -
FIGS. 10A and 10B are diagrams for explanation of a principle of a method of forming a magnetic film; -
FIGS. 11A to 11D are perspective views for explanation of a method of manufacturing the multilayered structure and a multilayered structure array according to the second embodiment of the present invention; -
FIGS. 12A to 12C are perspective views for explanation of the method of manufacturing the multilayered structure and the multilayered structure array according to the second embodiment of the present invention; -
FIG. 13 is a perspective view for explanation of the method of manufacturing the multilayered structure and the multilayered structure array according to the second embodiment of the present invention; -
FIGS. 14A and 14B are perspective views for explanation of a modified example of the method of manufacturing the multilayered structure and the multilayered structure array according to the second embodiment of the present invention; -
FIG. 15 is a sectional view for explanation of an interconnection method in a conventional multilayered structure; and -
FIG. 16 is a sectional view for explanation of another interconnection method in the conventional multilayered structure. - Hereinafter, preferred embodiments of the present invention will be described in detail by referring to the drawings. The same reference numerals are assigned to the same component elements and the description thereof will be omitted.
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FIG. 1 is a sectional view showing a multilayered structure according to one embodiment of the present invention. Themultilayered structure 1 is a columnar structure having a bottom surface with sides on the order of 0.2 mm to 1.0 mm, for example. In the embodiment, as a dielectric material, a piezoelectric material as a ferroelectric material is used. Themultilayered structure 1 includes plural piezoelectric material layers 10, plural internal electrode layers 11 a and 11 b, andcoatings 12 formed on one ends of the respective internal electrode layers 11 a and 11 b. Further, themultilayered structure 1 may include twoside electrodes multilayered structure 1 may include anupper electrode 14 and alower electrode 15 formed as external electrodes on upper and lower bottom surfaces of the stacked plural piezoelectric material layers 10, respectively. As shown inFIG. 1 , theupper electrode 14 is connected to oneside electrode 13 b and thelower electrode 15 is connected to the other side electrode 13 a. The shape of the bottom of themultilayered structure 1 is not limited to a square, but rectangular or other shapes may be adopted. Further, in the embodiment, although the side electrodes are disposed on opposed twoside surfaces - Each
piezoelectric material layer 10 is a piezoelectric material film having a thickness on the order of 100 μm. In the embodiment, PZT (Pb(lead) zirconate titanate) as a binary solid solution containing PbZrO3 and PbTiO3 as principal chemical compositions is used as the piezoelectric material. Further, a ternary or above solid solution (called as relaxer material) formed by adding at least one of Pb (Mg1/3Nb2/3)O3, Pb (Ni1/3Nb2/3)O3, Pb (Zn1/3Nb2/3)O3 as a third component to such a binary solid solution may be used. Alternatively, as the piezoelectric material, PLZT (lanthanum-doped lead zirconate titanate) formed by adding lanthanum oxide to PZT, or a non-lead piezoelectric material such as KNbO3 or bismuth series material may be used. Further, thepiezoelectric material layer 10 may contain not only those principal components but also elements such as germanium (Ge), silicon (Si), lithium (Li), bismuth (Bi), boron (B), and lead (Pb), which are contained in auxiliaries to be used for growing crystals by heat treatment. - Each of the internal electrode layers 11 a and 11 b has a thickness of about 2 μm. As the internal electrode layers 11 a and 11 b, hardly-oxidizable conducting materials may be desirably used, and platinum (Pt) is used in the embodiment.
- Further, each of the
coatings 12 is a film having a thickness of about 10 μm, and provided for insulating the internal electrode layers 11 a and 11 b from theside electrodes coatings 12 are formed by forming films of a conducting material by using an electrodeposition method on predetermined end surfaces of the internal electrode layers 11 a and 11 b, and then, causing the films to have insulation by oxidizing them. Accordingly, at least the surfaces of the coatings 12 (surfaces in contact with theside electrodes coatings 12, and at least the surfaces of thecoatings 12 are nickel oxide. Although the entire regions of thecoatings 12 have been made to have insulation inFIG. 1 , the conducting material may be left inside of thecoatings 12. Here, the electrodeposition method includes an electroplating, or a deposition method utilizing electrophoresis power. - On the
side surface 1 a of themultilayered structure 1, the end surfaces of the internal electrode layers 11 a are covered by thecoatings 12, and, on theside surface 1 b of themultilayered structure 1, the end surfaces of the internal electrode layers 11 b are covered by thecoatings 12. Thereby, the internal electrode layers 11 a are insulated from theside electrode 13 a located on theside surface 1 a, and the internal electrode layers 11 b are insulated from theside electrode 13 b located on theside surface 1 b. Since the electrodes of the multilayered structure are thus formed, the stacked plural layers are electrically connected in parallel. - By applying a voltage between the internal electrode layers 11 a and 11 b so that electric fields are applied to the respective piezoelectric material layers 10, the respective piezoelectric material layers 10 expand and contract by the piezoelectric effect. The multilayered structures employing such piezoelectric material layers as dielectric layers can be used for piezoelectric pumps, piezoelectric actuators, ultrasonic transducers for transmitting and receiving ultrasonic waves in an ultrasonic probe, and so on. Further, in the structure having the multilayered structure as described above, since areas of the opposed electrodes can be made larger than that in a single layer structure, electrical impedance can be made lower. Therefore, compared to the single layer structure, the multilayered structure operates more efficiently for the applied voltage.
- Next, a method of manufacturing a multilayered structure and a multilayered structure array according to a first embodiment of the present invention will be described by referring to
FIGS. 2A to 6C.FIGS. 2A to 6C are diagrams for explanation of the method of manufacturing a multilayered structure and a multilayered structure array according to the embodiment. - First, a workpiece in which plural piezoelectric material layers and plural electrode layers are stacked is fabricated. For the purpose, as shown in
FIG. 2A , apiezoelectric material layer 21 is formed on asubstrate 20. In this regard, in the embodiment, the aerosol deposition (AD) method is used. The AD method is a deposition method of spraying a raw material powder on a foundation layer at a high speed and depositing the raw material powder thereon, and also referred to as a gas deposition method, jet printing system, or injection deposition method. -
FIG. 7 is a schematic diagram showing a film forming device by using the AD method. This film forming device has anaerosol generating container 42 in which araw material powder 41 is placed. Here, an aerosol refers to fine particles of a solid or liquid floating in a gas. In theaerosol generating container 42, a carrier gas lead-inpart 43, an aerosol lead-outpart 44, and a vibratingpart 45 are provided. The carrier gas lead-inpart 43 introduces a gas such as a nitrogen gas (N2), and thereby, the raw material powder placed in theaerosol generating container 42 is blown up to generate the aerosol. Simultaneously, the vibratingpart 45 applies vibration to theaerosol generating container 42, and thereby, the raw material powder is agitated and the aerosol is efficiently generated. The generated aerosol is guided to afilm forming chamber 46 through the aerosol lead-outpart 44. - In the
film forming chamber 46, anexhaust pipe 47, anozzle 48, and amovable stage 49 are provided. Theexhaust pipe 47 is connected to a vacuum pump and exhausts air from thefilm forming chamber 46. Thenozzle 48 sprays the aerosol generated in theaerosol generating container 42 and introduced through the aerosol lead-inpart 44 into thefilm forming chamber 46 toward thesubstrate 20. Thesubstrate 20 is mounted on themovable stage 49 that is movable in a three-dimensional manner, and the relative position between thesubstrate 20 and thenozzle 48 is adjusted by controlling themovable stage 49. The particles (raw material powder) injected from thenozzle 48 and accelerated to a high speed with high kinetic energy collide against thesubstrate 20 are deposited thereon. It is thought that, at this time, the chemical reaction called mechanochemical reaction is caused by the collision energy of particles, and the particles are strongly attached to the substrate or previously formed films by the reaction. As thesubstrate 20, glass, quartz, ceramics such as PZT, metal such as SUS may be used, and glass is used in the embodiment. - As the
raw material 31, for example, a PZT monocrystal powder having an average particle diameter of 0.3 μis mixed in auxiliaries such as germanium, silicon, lithium, bismuth, boron, and lead used for growing crystals by heat treatment according to need and placed within theaerosol generating container 42 shown inFIG. 7 , and the film forming device is driven. Thereby, thepiezoelectric material layer 21 as shown inFIG. 2A is formed on thesubstrate 20. - Then, as shown in
FIG. 2B , a platinum layer of about 2 μm as anelectrode layer 22 is formed by sputtering or vacuum deposition on thepiezoelectric material layer 21. The thickness of theelectrode layer 22 is desirably 200 nm or more, and more preferably, 300 nm or more. The reason is that, in the case where the piezoelectric material layer is formed by the AD method on theelectrode layer 22, because a phenomenon called anchoring that the raw material powder cuts into the foundation layer occurs when the powder is sprayed on the foundation layer, considering the typical depth of anchoring on the order of 10 nm to 300 nm, the thickness at the above degree is required such that it may function as an electrode layer. - Further, the formation of the
piezoelectric material layer 21 shown inFIG. 2A and the formation of theelectrode layer 22 shown inFIG. 2B are repeated at required times and thepiezoelectric material layer 21 is formed at the uppermost layer, and thereby, aworkpiece 23 shown inFIG. 2C is formed. Here, the thickness of the lowermostpiezoelectric material layer 21 is made thicker than that of the other piezoelectric material layers 21 that will be formed later. For example, the thickness of the lowermostpiezoelectric material layer 21 is about 1000 μm or ten times that of the other piezoelectric material layers 21 (e.g., about 100 μm). - Subsequently, the
substrate 20 is removed by grinding or peeling from theworkpiece 23. Afterwards, a heat treatment step of theworkpiece 23 at predetermined temperature (e.g., about 500° C. to 1000° C.) may be provided in order to improve the piezoelectric performance by enlarging grain size of PZT contained in the piezoelectric material layers. - Furthermore, by dicing the work piece with a predetermined pitch to a predetermined depth in the direction shown by a broken line in
FIG. 2C , agroove 24 is formed and theworkpiece 23 is separated intoplural structures 25 that are partially connected to one another as shown inFIG. 3A . The width of thegroove 24 is made substantially equal to the element interval (e.g., about 50 μm) of the multilayered structure array to be fabricated. The outer side surface of theworkpiece 23 and the side surface newly exposed as thegroove 24 are formed make become surfaces on which the coatings 12 (FIG. 1 ) are to be formed. At the time of dicing, the contour of theworkpiece 23 orstructure 25 may be shaped such that the end surfaces of the electrode layers 22 may be positively exposed on the side surfaces. - Then, in the
structure 25, metal coatings are selectively formed on predetermined end surfaces of the plural electrode layers 22. As a material of coatings, a relatively easily-oxidizable metal is used, and nickel (Ni) is used in the embodiment. As shown inFIG. 3A , interconnections 26 are formed on the end surfaces of the electrode layers 22 by using a method such as wire bonding or solder joint from every other layer in eachstructure 25 as shown inFIG. 3A . The surface on which the interconnections are formed is desirably a surface other than the surface on which thecoatings 12 are to be formed, and they are formed on the front side surface in the drawing in the embodiment. Then, electroplating is performed using a plating solution containing nickel ions to attach nickel to the end surfaces of the electrode layers 22 on which theinterconnections 26 have been formed. Thus, as shown inFIG. 3B ,nickel coatings 27 of about 10 μm are formed on eachstructure 25. Then, theinterconnections 26 are removed. - Then, as shown in
FIG. 3C , the outer part and thegroove 24 of theplural structures 25, on which thenickel coatings 27 have been formed, are filled with anepoxy resin 28 and the resin is cured. Thereby, the side surfaces on which thenickel coatings 27 have been formed are protected. Then, agroove 29 is formed in eachstructure 25 by performing dicing in the direction of the broken line shown inFIG. 3B , and pluralrectangular structures 30 that are partially connected to one another are formed. In eachstructure 30, new end surfaces of the electrode layers 22 are exposed by thegroove 29. - Then, in the
structure 30, nickel coatings are selectively formed on predetermined end surfaces of the plural electrode layers 22. As shown inFIG. 4A , in eachstructure 30,interconnections 31 are formed on the end surfaces of the electrode layers 22, on which thenickel coating 27 is not formed, by using a method such as wire bonding or solder joint. Then, electroplating is performed by using a plating solution containing nickel ions to attach nickel to the end surfaces of the electrode layers 22 on which the interconnections have been formed. In this regard, since the surfaces on which thenickel coatings 27 have been previously formed are covered by theepoxy resin 28, no film is formed on the end surfaces of the electrode layers 22 even if theinterconnections 31 are formed. Thus, as shown inFIG. 4B ,nickel coatings 32 of about 10 μm are formed on eachstructure 30. Then, theinterconnections 31 are removed. - Then, the
plural structures 30 are immersed in an organic solvent such as acetone to dissolve theepoxy resin 28. Thereby,plural structures 30 in whichnickel coatings nickel coatings plural structures 30 for 30 minutes in air in an atmosphere at 800° C. Thereby, theplural structures 30 on which insulatingfilms 33 have been formed are obtained as shown inFIG. 4C . The heat treatment on the piezoelectric material layers may be simultaneously performed by controlling the temperature and time of that heat treatment. - Then, as shown in
FIG. 5A ,platinum films 34 of about 3 μm are formed around thestructures 30 by performing electroless platinum plating on theplural structures 30 on which the insulatingfilms 33 have been formed. Furthermore, as shown inFIG. 5B , insulatingregions 35 are formed by dicing and removing parts of theplatinum films 34 that have been formed on the top surfaces of thestructures 30 near the one surfaces on which the insulatingfilms 33 have been formed. Further, theplatinum films 34 formed on the side surfaces of thestructures 33 on which no insulatingfilm 33 has been formed (surfaces at the front side and the opposite side in the drawing) are removed by grinding. Theplatinum films 34 left thereby are used as two side electrodes and used as upper electrodes connected to one side electrode and insulated from the other side electrode. - Then, dicing is performed in the direction of the broken lines shown in
FIG. 5B (the direction perpendicular to the longitudinal sides of the rectangular shapes) to a predetermined depth. Thereby, as shown inFIG. 5C , pluralmultilayered structures 36 that are partially connected are obtained. In this regard, the bottom surface of eachmultilayered structure 36 can be made to have a square form by setting the pitch and width of dicing nearly equal to those formed between theplural structures 30. - Then, the grooves formed between the plural
multilayered structures 36 and surrounding parts are filled with a filling material such as anepoxy resin 37 and the material is cured as shown inFIG. 6A . As the filling material, urethane resin, silicone rubber, or the like may be used other than that. Then, the lower parts of the pluralmultilayered structures 36 in the drawing are ground to the region shown by a broken line. Thereby, the end surfaces of the piezoelectric material layers and side electrodes of eachmultilayered structure 36 are exposed on the lower bottom surface of theepoxy resin 37. Since the pluralmultilayered structures 36 are fixed by theepoxy resin 37, the matrix arrangement shown in the drawing is never out of alignment. - Then, as shown in
FIG. 6B , insulatingfilms 38 are formed at the bottom surface of theepoxy resin 37 so as to cover the end surfaces of the side electrodes at the side where they are connected to the upper electrodes. For this purpose, for example, silicon oxide films (SiO2) may be formed by sputtering using a metal mask. The insulatingfilms 38 are for insulating the side electrodes from a common electrode, which will be formed later, and may be formed continuously between elements having side electrodes to be insulated within the same plane. - Further, as shown in
FIG. 6C , acommon electrode 39 is formed by forming a film of gold (Au) by sputtering, for example, at the bottom surface of theepoxy resin 37. In this regard, the regions of the insulatingfilms 38 may be excluded from the film forming region by using a metal mask. - Thus, a multilayered structure array (1-3 composite) 2 including plural multilayered structures 1 (
FIG. 1 ) arranged in a two-dimensional manner can be manufactured. - In the case where a single multilayered structure is fabricated, the lower part of the plural
multilayered structures 36 fixed by theepoxy resin 37 are ground as shown inFIG. 6A , and then, the pluralmultilayered structures 36 are separated from one another by dissolving the epoxy resin using an organic solvent. According to need, lower electrodes or insulatingfilms 38 shown inFIG. 6B may be formed before dissolving the epoxy resin. - Furthermore, according to a similar method, a multilayered structure array including plural
multilayered structures 1 arranged in a one-dimensional manner can be also manufactured. - In the embodiment, dicing has been performed in the direction perpendicular to the longitudinal sides of the rectangular shapes as shown in
FIG. 5C . However, the direction may not be the perpendicular direction as long as each multilayered structure after separation includes two side electrodes. - Further, in the embodiment, the piezoelectric material layers in the
workpiece 23 have been formed by using the AD method. However, the same work piece can be fabricated by stacking PZT plate materials on which the metal thin films as electrode layers have been formed or stacking the PZT thick films and electrode layers using other methods than the AD method (e.g., green sheet method). - Next, another method of manufacturing the multilayered structure and the multilayered structure array according to the embodiment will be described.
- As shown in
FIG. 5B , after the upper electrodes and side electrodes are formed on theplural structures 30, the surrounding parts of theplural structures 30 and the grooves between the structures are filled with an epoxy resin and the resin is cured. Theplural structures 30 are separated from one another by grinding the lower part of theplural structures 30. Further, in the same way as have been described usingFIG. 6B , insulating films are formed on the end surfaces of one side electrodes exposed on the lower bottom surface of the epoxy resin, and further, a common electrode is formed. Thereby, a multilayered structure array in which plural rectangular multilayered structures are arranged in a one-dimensional manner can be fabricated. - Further, in order to fabricate a single rectangular multilayered structure, as shown in
FIG. 5B , after the upper electrodes and the side electrodes are formed on theplural structures 30, the surrounding parts of theplural structures 30 and the grooves between the structures are filled with an epoxy resin and the resin is cured. As the filling material, urethane resin, silicone rubber, or the like may be used other than that. Further, the lower part of the plural structures are ground 30 and theplural structures 30 may be separated from one another, and then, the epoxy resin is dissolved by an organic solvent. In this regard, according to need, lower electrodes or insulatingfilms 38 shown inFIG. 6B may be formed before dissolving the epoxy resin. - As described above, in the embodiment, the coatings formed on the side regions of the multilayered structure for insulating the side electrodes from the internal electrode layers are formed by forming films of a conducting material using an electrodeposition method and oxidizing the films. That is, since dense metal oxide covers the end surfaces of the internal electrodes, even the insulating films are as thin as about 10 μm, sufficient insulation performance can be exerted. Further, since the film thickness can be controlled, narrow pitch arrangement in a multilayered structure can be easily accommodated.
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FIG. 8 is a sectional view showing an ultrasonic probe using the multilayered structures according to the embodiment as an ultrasonic transducer array. As shown inFIG. 8 , this ultrasonic probe includes amultilayered structure array 2 shown inFIG. 6C ,interconnections 51 drawn from themultilayered structure array 2, anacoustic matching layer 52 of Pyrex glass or the like disposed at one bottom surface side (e.g., thecommon electrode 39 side) of themultilayered structure array 2, and abacking material 53 of an epoxy resin containing metal powder or the like disposed at the other bottom surface side. InFIG. 8 , a casing for accommodating the ultrasonic probe is omitted. - Since the electrical impedance can be lowered and impedance matching with a transmitting and receiving circuit can be improved using the above-mentioned multilayered structures as ultrasonic transducers used for an ultrasonic probe, application efficiency of voltage can be improved and detection sensitivity of ultrasonic waves can be made higher. Further, since the number of ultrasonic transducers to be mounted can be increased by narrowing the pitches of element arrangement in the ultrasonic transducer array, scanning density of ultrasonic waves can be made higher and the transmission and reception directions can be controlled more precisely. Therefore, the image quality of ultrasonic images can be improved by making solving power higher. Alternatively, the entire ultrasonic probe can be downsized while maintaining the conventional ultrasonic transmission and reception performance.
- Next, a multilayered structure according to a second embodiment of the present invention will be described.
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FIG. 9 is a sectional view showing a structure of the multilayered structure according to the second embodiment. Thismultilayered structure 3 hasinternal electrodes multilayered structure 1 shown inFIG. 1 and, in place of thecoatings 12,internal electrodes coatings 62. Other constitution is the same as that of themultilayered structure 1 shown inFIG. 1 . - In the embodiment, the
coatings 62 are formed by forming films of a conducting material on predetermined end surfaces of the internal electrode layers 61 a and 61 b, and then, making the films to have insulation by oxidizing them. However, the method of forming coatings differs from the method in the first embodiment. That is, in the embodiment, films are formed on the end surfaces of the internal electrode layers using magnetophoresis power in place of electrophoresis power. For this purpose, in each of the internal electrode layers 61 a and 61 b, conducting materials of different types are disposed such that a conducting material (first conducting materials 63) having magnetism extends to a side surface on which thecoatings 62 are to be formed and a conducting material (second conducting materials 64) having no magnetism extends to a side surface on which thecoatings 62 are not to be formed. Further, as a raw material of thecoatings 62 before insulation, a conducting material having magnetism is used. -
FIGS. 10A and 10B are diagrams for explanation of a principle of a method of forming insulating films by magnetophoresis. In a container shown inFIG. 10A , asuspension 6 in which particles of a conducting material having magnetism (hereinafter, referred to as magnetic particles) 4 are dispersed in a liquid 5 is placed. As the liquid 5, in order to smoothly cause the migration, a liquid having relatively low viscosity such as water, alcohol, toluene, or xylene is desirably used. - A laminated structure including plural piezoelectric material layers 10 and internal electrode layers 61 a and 61 b is put into the
suspension 6. As a result, themagnetic particles 4 are attracted by thefirst conducting materials 63 having magnetism according to the magnetophoresis power, and adhere to the end surfaces of thefirst conducting materials 63. Thereby, as shown inFIG. 10B , themagnetic films 65 can be selectively formed on one end surfaces of the respective internal electrode layers 61 a and 61 b. - As the first conducting material 63 (magnetic conducting material) and the magnetic particle 4 (magnetic conducting material), the following combinations (A) to (C) are conceivable.
- (A) spontaneous magnetization film as the first conducting
material 63 and single magnetic domain particle as themagnetic particle 4 - (B) spontaneous magnetization film as the first conducting
material 63 and multiple magnetic domain particle as themagnetic particle 4 - (C) multiple magnetic domain film as the first conducting
material 63 and single magnetic domain particle as themagnetic particle 4 - In the case of using the combination (A), the
magnetic particle 4 can be attached to the first conductingmaterial 63 relatively strongly. Further, in the case of using the combination (B), the handling of themagnetic particles 4 when thesuspension 6 is prepared is easy, and the power of migration is high and practical. Furthermore, in the case of using the combination (C), the step of placing the first conductingmaterial 63 on thepiezoelectric material layer 10 can be simplified. When the materials are determined, an appropriate combination may be selected in consideration of the size and shape of multilayered structure, the compatibility with the raw material of piezoelectric material layer, the manufacturing facility, or the like. Especially, it is necessary to note the relationship between heat treatment temperature for oxidizing themagnetic films 65 later and Curie points of the first conductingmaterial 63 and themagnetic particle 4. - As the first conducting
material 63, transition metal such as manganese (Mn), iron (Fe), cobalt (Co), and nickel (Ni) and a material containing them, or rare earth such as neodium (Nd) and samarium (Sm) and a material containing them is used. Specifically, a conducting material having magnetism such as iron-cobalt (permendur) alloy, samarium-cobalt alloy, neodium-iron-boron alloy, or tungsten steel is used. Further, as thesecond conducting material 64, a hardly-oxidizable non-magnetic material such as gold (e.g., Au) or platinum (e.g., Pt) is used. Furthermore, as themagnetic particle 4, a relatively easily-oxidizable magnetic material such as iron or nickel is used. In the embodiment, a combination of tungsten steel as thefirst conducting materials 63, platinum as thesecond conducting materials 64, and iron (Fe) as themagnetic particle 4 is adopted. It is desirable that the particle diameter of themagnetic particle 4 is made as small as possible so as to evenly cover the end surfaces of the internal electrode layers 61 a and 61 b (e.g. about 1 μm or less). - Next, a method of manufacturing the multilayered structure and the multilayered structure array according to the second embodiment of the present invention will be described by referring to
FIGS. 11A to 13. - First, a workpiece, in which plural piezoelectric material layers and internal electrode layers each containing two kinds of conducting materials are stacked, is fabricated. For this purpose, a
piezoelectric material layer 71 is formed on asubstrate 70 using the AD method as shown inFIG. 11A . - Then, as shown in
FIG. 11B , anelectrode layer 72 is formed by alternately disposing thefirst conducting materials 63 and thesecond conducting materials 64 in band forms on thepiezoelectric material layer 71. For this purpose, first, films of the first conducting materials 63 (tungsten steel) are formed by performing sputtering in the magnetic field using a metal mask in which slit-like openings have been formed at substantially equal widths and intervals to the width of themultilayered structure 3. Then, films of the second conducting materials (platinum) 64 are formed by performing sputtering or vacuum deposition using the metal mask after shifting thesubstrate 70 by a distance substantially equal to the width of themultilayered structure 3. By the way, as shown inFIG. 11B , the widths of thefirst conducting materials 63 and thesecond conducting materials 64 may be made narrower than the width of themultilayered structure 3 at both ends of theelectrode layer 72. Here, in order to form a spontaneous magnetization film as the first conducting material, not only the above-mentioned magnetic orientation film formation, but also epitaxial growth utilizing crystal magnetic anisotropy and shape magnetic anisotropy may be performed. - Then, as shown in
FIG. 1C , thepiezoelectric material layer 71 is formed using AD method on theelectrode layer 72. - Then, as shown in
FIG. 1D , anelectrode layer 73 is formed by alternately disposing thefirst conducting materials 63 and thesecond conducting materials 64 in band forms on thepiezoelectric material layer 71. In this regard, the locational relationship between thefirst conducting materials 63 and thesecond conducting materials 64 is made opposite to the locational relationship between them in theelectrode layer 72. The method of forming thefirst conducting materials 63 and thesecond conducting materials 64 is the same as that in theelectrode layer 72. - Furthermore, the steps shown in
FIGS. 11A to 11D are repeated at required times and thepiezoelectric material layer 71 is formed on the uppermost position, and thereby, aworkpiece 74 shown inFIG. 12A is formed. Subsequently, thesubstrate 70 is removed by grinding or peeling from theworkpiece 74. A heat treatment step of theworkpiece 74 at predetermined temperature (e.g., 500° C. to 1000° C.) may be provided afterwards in order to improve the piezoelectric performance by enlarging grain size of PZT contained in the piezoelectric material layers. - Then, as shown by broken lines in
FIG. 12A , theworkpiece 74 is separated into plural rectangular structures that are partially connected by dicing the workpiece at the substantially central parts of thefirst conducting materials 63 and substantially central part of thesecond conducting materials 64 in the longitudinal direction of the conducting materials. As shown inFIG. 12B , in the respectiverectangular structures 75, the locational relationships between thefirst conducting materials 63 and thesecond conducting materials 64 in theinternal electrode 61 a and theinternal electrode 61 b are opposite to each other. At the time of dicing, the contour of theworkpiece 74 may be shaped such that the end surfaces of thefirst conducting materials 63 and thesecond conducting materials 64 may be positively exposed on the side surfaces of theworkpiece 74. - Then, as shown in
FIG. 12C , the pluralrectangular structures 75 are immersed in asuspension 6 in which an iron fine powder as magnetic particles is dispersed in a liquid. Thereby, magnetic particles migrate by magnetism and adhere to the end surfaces of thefirst conducting materials 63 exposed on the side surfaces of therespective structures 75. As a result,magnetic films 76 are formed as shown inFIG. 13 . - Then, the
magnetic films 76 are oxidized by heat treating theplural structures 75 on which themagnetic films 76 have been formed for 30 minutes in air in an atmosphere at 800° C. As a result, thestructures 75 on which insulating films have been formed on the predetermined end surfaces of internal electrodes can be obtained. The steps of manufacturing a multilayered structure array or single multilayered structure from thosestructures 75 are the same as those have been described in the first embodiment by referringFIGS. 4C to 6C. - Next, a modified example of the method of manufacturing the multilayered structure and the multilayered structure array according to the embodiment will be described. In this modified example, as shown in
FIG. 14A , two kinds of the first andsecond conducting materials first conducting materials 63 and thesecond conducting materials 64 may overlap between electrode layers 81 and electrode layers 82, which will be formed alternately. When the multilayered structure including plural piezoelectric material layers and plural electrode layers is separated into plural multilayered structures, dicing is performed at those boundaries (broken line positions inFIG. 14A ). As shown inFIG. 14B , since the insulating films are formed in a staggered manner on two side surfaces opposed with grooves in between in the case where the electrode layers are thus disposed, the plural multilayered structures can be arranged with narrower pitches. - The arrangement of the two kinds of conducting materials that form the internal electrode layers are not necessarily band forms as shown in
FIGS. 11B, 11D and 14A, but an arbitrary arrangement may be adopted in accordance to the shape (e.g., cylindrical shape) or arrangement (e.g., concentric or random arrangement) of multilayered structures to be fabricated. That is, it is essential only that the conducting materials having magnetism be disposed at the side surface side where the insulating films are formed. In this case, two kinds of patterns of conducting materials can be formed using a metal mask. Further, the multilayered structures may be shaped or separated so as to be in arbitrary shapes or arrangement using the sandblasting method. - Next, a second modified example of the method of manufacturing the multilayered structure and the multilayered structure array according to the embodiment will be described.
- In the modified example, as the first conducting
material 63 and thesecond conducting material 64 that form the internal electrode layers, metals or alloys both having magnetism at normal temperature but having different Curie points are used. That is,multilayered structures 75 shown inFIG. 12B are fabricated by employing a material “A” having Curie point TCA as thefirst conducting materials 63 on which thecoatings 62 are formed, and a material “B” having Curie point TCB (TCB<TCA) as thesecond conducting materials 64 on which nocoating 62 is formed. When magnetophoresis is performed, the temperature of the liquid in which magnetic particles have been dispersed is held at temperature T between TCA and TCB (TCB<T<TCA). Thereby, since the spontaneous magnetization of the material “B” becomes zero, the magnetic particles do not adhere to the end surfaces of the material “B”, and insulating films can be selectively formed only on the end surfaces of the material “A”. As the combination of material “A” and material “B”, for example, permendur (Curie point 980° C.) and nickel (Curie point 354° C.) may be used. - Thus, by controlling the expression of magnetism with temperature, the range of choice of materials that can be used as conducting materials can be expanded. Further, the expression of magnetism may be controlled not only with Curie point, but also with structural phase transition temperature or glass transition point.
- Thus, according to the embodiment, coatings can be easily formed on the end surfaces of internal electrode layers using magnetophoresis. Accordingly, even in the case where opposed electrodes for electrophoresis are difficult to be disposed because of size or arrangement of multilayered structures in the multilayered structure array, coatings can be easily formed on the end surfaces of internal electrode layers of each multilayered structure.
- In the above-mentioned first and second embodiments of the present invention, oxidization treatment has been performed in order to make the coatings of the conducting materials covering the end surfaces of the internal electrode layers to have insulation, not only the oxidization treatment but also nitriding treatment, fluorination treatment, or sulfuration treatment may be used. For example, in the case of using fluorination treatment, nickel films are formed on the end surfaces of the internal electrode layers, the nickel films are chloridized using hydrochloric acid, and then, fluorine is allowed to act thereon in an atmosphere at 150° C. Thereby, nickel fluoride (NiFe2) having insulation can be formed.
- Further, in the first and second embodiments of the present invention, dicing has been performed while not completely separating the workpiece shown in
FIGS. 2C and 12A or the like in order to hold the arrangement of the plural multilayered structures in a finished product. However, the manufacturing process may be advanced with the substrate used at the time of workpiece formation mounted. In this case, when the workpiece is divided into plural structures, the dicing may be performed to the lower bottom surface of the workpiece. Further, in the case, the plural structures can be completely separated from one another by removing the substrate by peeling or grinding.
Claims (20)
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